U.S. patent application number 11/204460 was filed with the patent office on 2005-12-08 for polycarbonate compositions.
Invention is credited to Irick, Gether JR., McWilliams, Douglas Stephens, Pearson, Jason Clay, Weaver, Max Allen.
Application Number | 20050272840 11/204460 |
Document ID | / |
Family ID | 35449882 |
Filed Date | 2005-12-08 |
United States Patent
Application |
20050272840 |
Kind Code |
A1 |
Pearson, Jason Clay ; et
al. |
December 8, 2005 |
Polycarbonate compositions
Abstract
This invention relates to polycarbonate compositions comprising:
(A) at least one polycarbonate comprising repeating units derived
from a dihydroxyaromatic compound or a dihydroxyaliphatic compound
of the formula HO--Y--OH; and (B) at least one salt prepared from
the reaction of one or more acidic phosphorus-containing compounds
and one or more hindered amine light stabilizers. The polycarbonate
compositions exhibit improved hydrolytic stability.
Inventors: |
Pearson, Jason Clay;
(Kingsport, TN) ; McWilliams, Douglas Stephens;
(Kingsport, TN) ; Irick, Gether JR.; (Gray,
TN) ; Weaver, Max Allen; (Kingsport, TN) |
Correspondence
Address: |
B. J. Boshears
Eastman Chemical Company
P.O. Box 511
Kingsport
TN
37662-5075
US
|
Family ID: |
35449882 |
Appl. No.: |
11/204460 |
Filed: |
August 16, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11204460 |
Aug 16, 2005 |
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10639712 |
Mar 5, 2003 |
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60439681 |
Jan 13, 2003 |
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Current U.S.
Class: |
524/115 |
Current CPC
Class: |
C08K 5/5205 20130101;
C08L 69/00 20130101; C08K 5/5205 20130101 |
Class at
Publication: |
524/115 |
International
Class: |
C08K 005/34 |
Claims
We claim:
1. A polymer composition comprising: (A) at least one
polycarbonate; and (B) at least one salt prepared by the reaction
of one or more acidic phosphorus-containing compounds with one or
more hindered amine light stabilizers.
2. A polymer composition according to claim 1 wherein the acidic
phosphorus compounds are selected from the compounds having the
formulas: 9wherein R.sub.1 and R.sub.2 are independently selected
from hydrogen, C.sub.1-C.sub.22-alkyl, substituted
C.sub.1-C.sub.22-alkyl, C.sub.3-C.sub.8-cycloalkyl, substituted
C.sub.3-C.sub.8-cycloalkyl, heteroaryl, and aryl; n is 2 to 500;
and X is selected from hydrogen and hydroxy; and wherein the
hindered amine light stabilizers selected from compounds having the
formulas: 101112Wherein R.sub.1 and R.sub.2 are independently
selected from hydrogen, C.sub.1-C.sub.22-alkyl, substituted
C.sub.1-C.sub.22-alkyl, C.sub.3-C.sub.8-cycloalkyl, substituted
C.sub.3-C.sub.8-cycloalkyl, heteroaryl, and aryl; R.sub.3, R.sub.4,
R.sub.5, and R.sub.6 are independently selected from hydrogen,
C.sub.1-C.sub.22-alkyl, substituted C.sub.1-C.sub.22-alkyl,
C.sub.3-C.sub.8-cycloalkyl, substituted C.sub.3-C.sub.8-cycloalkyl,
heteroaryl, aryl; R.sub.7 is selected from hydrogen, --OR.sub.6,
C.sub.1-C.sub.22-alkyl, substituted C.sub.1-C.sub.22-alkyl,
C.sub.3-C.sub.8-cycloalkyl, substituted C.sub.3-C.sub.8-cycloalkyl;
R.sub.8 is selected from hydrogen; C.sub.1-C.sub.22-alkyl,
substituted C.sub.1-C.sub.22-alkyl, C.sub.3-C.sub.8-cycloalkyl,
substituted C.sub.3-C.sub.8-cycloalkyl, heteroaryl, aryl,
--Y.sub.1--R.sub.1 or a succinimido group having the formula
13R.sub.9 and R.sub.10 are independently selected from hydrogen,
C.sub.1-C.sub.22-alkyl, substituted C.sub.1-C.sub.22-alkyl,
C.sub.3-C.sub.8-cycloalkyl, and substituted
C.sub.3-C.sub.8-cycloalkyl; R.sub.9 and R.sub.10 may collectively
represent a divalent group forming a ring with the nitrogen atom to
which they are attached, e.g., morpholino, piperidino and the like;
L.sub.1 is a divalent linking group selected from
C.sub.2-C.sub.22-alkylene;
--(CH.sub.2CH.sub.2--Y).sub.1-3--CH.sub.2CH.sub.2--;
C.sub.3-C.sub.8-cycloalkylene; arylene; or --CO-L.sub.2-OC--;
L.sub.2 is selected from C.sub.1-C.sub.22-alkylene, arylene,
--(CH.sub.2CH.sub.2--Y.- sub.1).sub.1-3--CH.sub.2CH.sub.2-- and
C.sub.3-C.sub.8-cycloalkylene; Y.sub.1 is selected from --OC(O)--,
--NHC(O)--, --O--, --S--, --N(R.sub.1)--; Y.sub.2 is selected from
--O-- or --N(R.sub.1)--; Z is a positive integer of up to about 20,
preferably up to about 6; m1, is selected from 0 to about 10; n1 is
a positive integer selected from 2 to about 12; R.sub.11, and
R.sub.12 are independently selected from hydrogen,
C.sub.1-C.sub.22-alkyl, substituted C.sub.1-C.sub.22-alkyl,
C.sub.3-C.sub.8-cycloalkyl, substituted C.sub.3-C.sub.8-cycloalkyl,
heteroaryl, aryl, and radical A wherein radical A is selected from
the following structures: 14Radical A structures wherein *
designates the position of attachment. wherein at least one of
R.sub.11 and R.sub.12 is an A radical; and wherein the ratio of the
number of phosphorus atoms in the acidic phosphorus-containing
compound to the number of basic nitrogen atoms in the HALS is about
0.25 to about 2, preferably from about 0.5 to about 1.1
3. A polymer composition comprising: (A) at least one
polycarbonate; and (B) about 0.01 to about 0.25 weight percent
based on the total weight of the polycarbonate composition of at
least one salt prepared by the reaction of one or more acidic
phosphorus-containing compounds selected from phosphorous acid,
phosphoric acid and polyphosphoric acid with one or more hinder
light amine stabilizers of claim 2.
4. A composition according to claim 3 wherein component B comprises
about 0.05 to about 0.15 weight percent based on the total weight
of the polycarbonate composition of at least one said salt wherein
R.sub.7 is hydrogen or alkyl and the ratio of the number of
phosphorus atoms in the acidic phosphorous-containing compound to
number of basic nitrogen atoms in the hindered amine light
stabilizer compound is about 0.25 to about 1.1.
5. A polymer composition comprising: (A) at least one
polycarbonate; and (B) about 0.01 to about 0.25 weight percent
based on the total weight of the composition of at least one salt
prepared by the reaction of phosphorous acid with one or more
hindered amine light stabilizers of the formulas: 1516Wherein
R.sub.1 and R.sub.2 are independently selected from hydrogen,
C.sub.1-C.sub.22-alkyl, substituted C.sub.1-C.sub.22-alkyl,
C.sub.3-C.sub.8-cycloalkyl, substituted C.sub.3-C.sub.8-cycloalkyl,
heteroaryl, and aryl; R.sub.3, R.sub.4, R.sub.5, and R.sub.6 are
independently selected from hydrogen, C.sub.1-C.sub.22-alkyl,
substituted C.sub.1-C.sub.22-alkyl, C.sub.3-C.sub.8-cycloalkyl,
substituted C.sub.3-C.sub.8-cycloalkyl, heteroaryl, aryl; R.sub.7
is selected from hydrogen, --OR.sub.6, C.sub.1-C.sub.22-alkyl,
substituted C.sub.1-C.sub.22-alkyl, C.sub.3-C.sub.8-cycloalkyl,
substituted C.sub.3-C.sub.8-cycloalkyl; R.sub.8 is selected from
hydrogen; C.sub.1-C.sub.22-alkyl, substituted
C.sub.1-C.sub.22-alkyl, C.sub.3-C.sub.8-cycloalkyl, substituted
C.sub.3-C.sub.8-cycloalkyl, heteroaryl, aryl, --Y.sub.1--R.sub.1 or
a succinimido group having the formula 17R.sub.9 and R.sub.10 are
independently selected from hydrogen, C.sub.1-C.sub.22-alkyl,
substituted C.sub.1-C.sub.22-alkyl, C.sub.3-C.sub.8-cycloalkyl, and
substituted C.sub.3-C.sub.8-cycloalkyl; R.sub.9 and R.sub.10 may
collectively represent a divalent group forming a ring with the
nitrogen atom to which they are attached, e.g., morpholino,
piperidino and the like; L.sub.1 is a divalent linking group
selected from C.sub.2-C.sub.22-alkylene;
--(CH.sub.2CH.sub.2--Y.sub.1).sub.1-3--CH.sub.2CH.sub.2--;
C.sub.3-C.sub.8-cycloalkylene; arylene; or --CO-L.sub.2-OC--;
L.sub.2 is selected from C.sub.1-C.sub.22-alkylene, arylene,
--(CH.sub.2CH.sub.2--Y.- sub.1).sub.1-3--CH.sub.2CH.sub.2-- and
C.sub.3-C.sub.8-cycloalkylene; Y.sub.1 is selected from --OC(O)--,
--NHC(O)--, --O--, --S--, --N(R.sub.1)--; Y.sub.2 is selected from
--O-- or --N(R.sub.1)--; Z is a positive integer of up to about 20,
preferably up to about 6; m1, is selected from 0 to about 10; n1 is
a positive integer selected from 2 to about 12; R.sub.11, and
R.sub.12 are independently selected from hydrogen,
C.sub.1-C.sub.22-alkyl, substituted C.sub.1-C.sub.22-alkyl,
C.sub.3-C.sub.8-cycloalkyl, substituted C.sub.3-C.sub.8-cycloalkyl,
heteroaryl, aryl, and radical A wherein radical A is selected from
the following structures: 18Radical A structures wherein *
designates the position of attachment. wherein at least one of
R.sub.1 and R.sub.12 is an A radical; and wherein the ratio of the
number of phosphorus atoms in the acidic phosphorus-containing
compound to the number of basic nitrogen atoms in the HALS is about
0.25 to about 2, preferably from about 0.5 to about 1.1.
6. A polymer composition comprising: (A) at least one
polycarbonate; and (B) about 0.01 to about 0.25 weight percent
based on the total weight of the composition of at least one salt
prepared by the reaction of phosphorous acid with a hindered amine
light stabilizer having the formula: 19wherein: R.sub.1 is
independently selected from hydrogen, C.sub.1-C.sub.22-alkyl,
substituted C.sub.1-C.sub.22-alkyl, C.sub.3-C.sub.8-cycloalkyl,
substituted C.sub.3-C.sub.8-cycloalkyl, heteroaryl, and aryl;
R.sub.3, R.sub.4, R.sub.5, and R.sub.6 are independently selected
from hydrogen, C.sub.1-C.sub.22-alkyl, substituted
C.sub.1-C.sub.22-alkyl, C.sub.3-C.sub.8-cycloalkyl, substituted
C.sub.3-C.sub.8-cycloalkyl, heteroaryl, aryl; R.sub.7 is selected
from hydrogen or --C.sub.1-C.sub.22-alkyl; R.sub.9 and R.sub.10 are
independently selected from hydrogen, C.sub.1-C.sub.22-alkyl,
substituted C.sub.1-C.sub.22-alkyl, C.sub.3-C.sub.8-cycloalkyl, and
substituted C.sub.3-C.sub.8-cycloalkyl wherein at least one of
R.sub.9 and R.sub.10 is a substituent other than hydrogen; R.sub.9
and R.sub.10 may collectively represent a divalent group forming a
ring with the nitrogen atom to which they are attached: L.sub.1 is
a divalent linking group selected from C.sub.2-C.sub.22-alkylene;
--(CH.sub.2CH.sub.2--Y.sub.1).su- b.1-3--CH.sub.2CH.sub.2--;
C.sub.3-C.sub.8-cycloalkylene; arylene; or --CO-L.sub.2-OC--; and
L.sub.2 is selected from C.sub.1-C.sub.22-alkylene- , arylene,
--(CH.sub.2CH.sub.2--Y.sub.1).sub.1-3--CH.sub.2CH.sub.2-- and
C.sub.3-C.sub.8-cycloalkylene; Y.sub.1 is selected from --OC(O)--,
--NHC(O)--, --O--, --S--, --N(R.sub.1)--; and Z is a positive
integer of up to about 6.
7. A composition according to claim 6 wherein component (B)
comprises about 0.05 to about 0.15 weight percent based on the
total weight of the composition of said salt wherein
R.sub.3=R.sub.4=R.sub.5=R.sub.6=R.sub.7=- methyl; L.sub.1 is
hexamethylene; and (R.sub.9)(R.sub.10)N-- collectively represent a
morpholino group and the ratio of the number of phosphorus atoms in
the phosphorous acid to number of basic nitrogen atoms in the
hindered amine light stabilizer is about 0.25 to about 1.1.
8. A composition according to claim 7 wherein component (B)
comprises about 0.05 to about 0.15 weight percent based on the
total weight of the composition of at least one said salt wherein
the ratio of the number of phosphorus atoms in the phosphorous acid
to number of basic nitrogen atoms in the hindered amine light
stabilizer is about 0.25 to about 0.6.
Description
RELATED APPLICATONS
[0001] This application claims priority to and the benefit of the
following applications; U.S. Patent Ser. No. 60/439,681 filed Jan.
13, 2003, incorporated herein by reference; and U.S. patent Ser.
No. 10/379,649 filed Mar. 5, 2003, incorporated herein by
reference.
FIELD OF THE INVENTION
[0002] This invention relates to a polymer composition comprising
(A) at least one polycarbonate; and (B) one or more salts composed
of at least one suitable phosphorus-containing acid and at least
one suitable hindered amine light stabilizer.
BACKGROUND OF THE INVENTION
[0003] Hydrolytic stability is a physical characteristic commonly
sought in polymers. It is therefore desirable to find methods for
providing polymer compositions with greater hydrolytic stability
and that are less detrimental to process equipment.
[0004] U.S. Pat. No. 4,619,956 discloses the combination of
2,2,6,6-tetraalkylpiperidine hindered amine light stabilizers
(HALS) and/or their addition salts with triazine ultraviolet
absorbers for stabilizing thermoset acrylic and alkyd coatings.
U.S. Pat. No. 5,714,530 discloses the utility of combining
non-polymeric 2,2,6,6,-tetraalkylpiper- idine HALS salts and/or
their acid addition salts with triazine ultraviolet light absorbers
for stabilizing certain polymer compositions. U.S. Pat. No.
6,051,164 discloses the use of a polymer stabilizing system
comprising from about 50 to about 5,000 ppm of at least one ortho
hydroxyl tris-aryl triazine light absorber and from about 500 ppm
to about 1.25 percent of at least one oligomer, polymeric or high
molecular weight HALS having a molecular weight of at least about
500, wherein the weight ratio of HALS to triazine light absorber is
from about 3:1 to about 20:1.
[0005] The detrimental effect of phosphorus-containing additives on
the hydrolytic stability of polycarbonate and
polycarbonate-polyester blends is disclosed in U.S. Pat. Nos.
4,456,717, 5,354,791, 5,744,526, 6,103,796, 4,393,158, and
6,107,375. Improved hydrolytic stability for polycarbonates
stabilized with phosphorus-containing compounds and siloxanes
containing oxetane groups are disclosed in U.S. Pat. No. 4,456,717.
Improved hydrolytic stability for polycarbonates stabilized with
phosphorus-containing compounds and an oligomer or polymer
containing at least one pendant cyclic iminoether group per
molecule is disclosed in U.S. Pat. No. 6,107,375. Improved
hydrolytic stability for polycarbonates stabilized with
phosphorus-containing compounds and an epoxy compound is disclosed
in U.S. Pat. No. 4,393,158. Improved hydrolytic stability for
polycarbonate-polyester blends stabilized with
phosphorus-containing compounds and a polyester having epoxy
functionality is disclosed in U.S. Pat. No. 5,354,791. Improved
hydrolytic stability for polycarbonates stabilized with
phosphorus-containing compounds and hexamethylene tetra amine is
disclosed in U.S. Pat. No. 5,744,526. Specifically, U.S. Pat. No.
5,744,526 teaches the addition of the amine to stabilize the
phosphite against hydrolysis and consequently improving the
hydrolytic stability of the polycarbonate composition.
[0006] This present invention relates to polycarbonates and the
unexpected improvements in hydrolytic stability for polycarbonates
containing an acidic phosphorous compound and a hindered amine
light stabilizers (HALS).
SUMMARY OF THE INVENTION
[0007] We have discovered that the presence of certain salts in
polycarbonates result in polymer compositions that exhibit improved
hydrolytic stability and that are less detrimental to process
equipment. The salts useful in the present invention are reaction
products of a suitable inorganic acid, such as a phosphorous acid,
with a suitable hindered amine light stabilizers (HALS).
[0008] Thus, the present invention provides a polymer composition
comprising:
[0009] (A) at least one polycarbonate; and
[0010] (B) at least one salt prepared by the reaction of one or
more acidic phosphorus-containing compounds with one or more
hindered amine light stabilizers.
[0011] Another embodiment of the present invention is a polymer
concentrate comprising:
[0012] (A) at least one polycarbonate; and
[0013] (B) up to about 10 weight percent, preferably about 5 to 10
weight percent based on the total weight of the polycarbonate of at
least one salt prepared by the reaction of one or more acidic
phosphorus-containing compounds and one or more hindered amine
light stabilizers.
DETAILED DESCRIPTION OF THE INVENTION
[0014] The present invention provides a polymer composition
comprising:
[0015] (A) at least one polycarbonate; and
[0016] (B) a salt prepared by the reaction of one or more acidic
phosphorus-containing compounds with one or more hindered amine
light stabilizers, wherein the phosphorus-containing compounds are
selected from compounds having the formula: 1
[0017] wherein
[0018] R.sub.1 and R.sub.2 are independently selected from
hydrogen, C.sub.1-C.sub.22-alkyl, substituted
C.sub.1-C.sub.22-alkyl, C.sub.3-C.sub.8-cycloalkyl, substituted
C.sub.3-C.sub.8-cycloalkyl, heteroaryl, and aryl;
[0019] n is 2 to 500; and
[0020] X is selected from hydrogen and hydroxy;
[0021] and wherein the hindered amine light stabilizers (HALS)
selected from compounds having the formulas: 2345
[0022] wherein
[0023] R.sub.1 and R.sub.2 are independently selected from
hydrogen, C.sub.1-C.sub.22-alkyl, substituted
C.sub.1-C.sub.22-alkyl, C.sub.3-C.sub.8-cycloalkyl, substituted
C.sub.3-C.sub.8-cycloalkyl, heteroaryl, and aryl;
[0024] R.sub.3, R.sub.4, R.sub.5, and R.sub.6 are independently
selected from hydrogen, C.sub.1-C.sub.22-alkyl, substituted
C.sub.1-C.sub.22-alkyl, C.sub.3-C.sub.8-cycloalkyl, substituted
C.sub.3-C.sub.8-cycloalkyl, heteroaryl, aryl;
[0025] R.sub.7 is selected from hydrogen, --OR.sub.6,
C.sub.1-C.sub.22-alkyl, substituted C.sub.1-C.sub.22-alkyl,
C.sub.3-C.sub.8-cycloalkyl, substituted
C.sub.3-C.sub.8-cycloalkyl;
[0026] R.sub.8 is selected from hydrogen; C.sub.1-C.sub.22-alkyl,
substituted C.sub.1-C.sub.22-alkyl, C.sub.3-C.sub.8-cycloalkyl,
substituted C.sub.3-C.sub.8-cycloalkyl, heteroaryl, aryl,
--Y.sub.1--R.sub.1 or a succinimido group having the formula 6
[0027] R.sub.9 and R.sub.10 are independently selected from
hydrogen, C.sub.1-C.sub.22-alkyl, substituted
C.sub.1-C.sub.22-alkyl, C.sub.3-C.sub.8-cycloalkyl, and substituted
C.sub.3-C.sub.8-cycloalkyl; R.sub.9 and R.sub.10 may collectively
represent a divalent group forming a ring with the nitrogen atom to
which they are attached, e.g., morpholino, piperidino and the
like;
[0028] L.sub.1 is a divalent linking group selected from
C.sub.2-C.sub.22-alkylene;
--(CH.sub.2CH.sub.2--Y.sub.1).sub.1-3--CH.sub.- 2CH.sub.2--;
C.sub.3-C.sub.8-cycloalkylene; arylene; or --CO-L.sub.2-OC--;
[0029] L.sub.2, L.sub.2' and L.sub.2" are independently selected
from C.sub.1-C.sub.22-alkylene, arylene,
--(CH.sub.2CH.sub.2--Y.sub.1).sub.1-3- --CH.sub.2CH.sub.2-- and
C.sub.3-C.sub.8-cycloalkylene;
[0030] Y.sub.1 is selected from --OC(O)--, --NHC(O)--, --O--,
--S--, --N(R.sub.1)--;
[0031] Y.sub.2 is selected from --O-- or --N(R.sub.1)--;
[0032] Z is a positive integer of up to about 20, preferably up to
about 6;
[0033] m1 is selected from 0 to about 10;
[0034] n1 is a positive integer selected from 2 to about 12;
[0035] R.sub.11, R.sub.11', R.sub.12, and R.sub.12' are
independently selected from hydrogen, C.sub.1-C.sub.22-alkyl,
substituted C.sub.1-C.sub.22-alkyl, C.sub.3-C.sub.8-cycloalkyl,
substituted C.sub.3-C.sub.8-cycloalkyl, heteroaryl, aryl, and
radical A;
[0036] wherein radical A for R.sub.11, R.sub.11', R.sub.12, and
R.sub.12' are independently selected from the following structures:
7
[0037] Radical A structures wherein * designates the position of
attachment;
[0038] wherein at least one of R.sub.11, R.sub.11', R.sub.12, and
R.sub.12' is an A radical; and wherein the ratio of the number of
phosphorus atoms in the acidic phosphorus-containing compound to
the number of basic nitrogen atoms in the HALS is about 0.25 to
about 2, preferably from about 0.5 to about 1.1
[0039] The term "C.sub.1-C.sub.22-alkyl" denotes a saturated
hydrocarbon radical which contains one to twenty-two carbons and
which may be straight or branched-chain. Such C.sub.1-C.sub.22
alkyl groups can be methyl, ethyl, propyl, butyl, pentyl, hexyl,
heptyl, octyl, isopropyl, isobutyl, tertbutyl, neopentyl,
2-ethylheptyl, 2-ethylhexyl, and the like. The term "substituted
C.sub.1-C.sub.22-alkyl" refers to C.sub.1-C.sub.22-alkyl radicals
as described above which may be substituted with one or more
substituents selected from hydroxy, halogen, cyano, aryl,
heteroaryl, C.sub.3-C.sub.8-cycloalkyl, substituted
C.sub.3-C.sub.8-cycloalkyl, C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6
alkanoyloxy and the like.
[0040] The term "C.sub.3-C.sub.8-cycloalkyl" is used to denote a
cycloaliphatic hydrocarbon radical containing three to eight carbon
atoms. The term "substituted C.sub.3-C.sub.8-cycloalkyl" is used to
describe a C.sub.3-C.sub.8-cycloalkyl radical as detailed above
containing at least one group selected from C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy, hydroxy, halogen, and the like.
[0041] The term "aryl" is used to denote an aromatic radical
containing 6, 10 or 14 carbon atoms in the conjugated aromatic ring
structure and these radicals substituted with one or more groups
selected from C.sub.1-C.sub.6-alkyl; C.sub.1-C.sub.6-alkoxy;
phenyl, and phenyl substituted with C.sub.1-C.sub.6-alkyl;
C.sub.1-C.sub.6-alkoxy; halogen and the like;
C.sub.3-C.sub.8-cycloalkyl; halogen; hydroxy, cyano,
trifluoromethyl and the like. Typical aryl groups include phenyl,
naphthyl, phenylnaphthyl, anthryl (anthracenyl) and the like. The
term "heteroaryl" is used to describe conjugated cyclic radicals
containing at least one hetero atom selected from sulfur, oxygen,
nitrogen or a combination of these in combination with from two to
about ten carbon atoms and these heteroaryl radicals substituted
with the groups mentioned above as possible substituents on the
aryl radical. Typical heteroaryl radicals include: 2- and 3-furyl,
2- and 3-thienyl, 2- and 3-pyrrolyl, 2-, 3-, and 4-pyridyl,
benzothiophen-2-yl; benzothiazol-2-yl, benzoxazol-2-yl,
benzimidazol-2-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl,
1,2,4-thiadiazol-5-yl, isothiazol-5-yl, imidazol-2-yl, quinolyl and
the like.
[0042] The terms "C.sub.1-C.sub.6-alkoxy" and
"C.sub.2-C.sub.6-alkanoyloxy- " are used to represent the groups
--O--C.sub.1-C.sub.6-alkyl and --OCOC.sub.1-C.sub.6-alkyl,
respectively, wherein "C.sub.1-C.sub.6-alkyl" denotes a saturated
hydrocarbon that contains 1-6 carbon atoms, which may be straight
or branched-chain, and which may be further substituted with one or
more groups selected from halogen, methoxy, ethoxy, phenyl,
hydroxy, acetyloxy and propionyloxy. The term "halogen" is used to
represent fluorine, chlorine, bromine, and iodine; however,
chlorine and bromine are preferred.
[0043] The term "C.sub.2-C.sub.22-alkylene" is used to denote a
divalent hydrocarbon radical that contains from two to twenty-two
carbons and which may be straight or branched chain and which may
be substituted with one or more substituents selected from hydroxy,
halogen, C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkanolyloxy and
aryl. The term "C.sub.3-C.sub.8-cycloalkylene" is used to denote
divalent cycloaliphatic radicals containing three to eight carbon
atoms and these are optionally substituted with one or more
C.sub.1-C.sub.6-alkyl groups. The term "arylene" is used to denote
1,2-, 1,3-, and 1,4-phenylene radicals and these optionally
substituted with C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy and
halogen.
[0044] The salt of component (B) of the novel compositions provided
by the present invention may be prepared by bringing together the
acidic phosphorus-containing compound and the hindered amine light
stabilizer in a suitable manner. A suitable manner is any procedure
that involves contacting the acidic phosphorus-containing acid with
the hindered amine light stabilizer. For example, the acidic
phosphorus-containing compound and the hindered amine light
stabilizer may be dissolved in an appropriate solvents and the
solutions mixed followed by precipitation of the reaction product;
mixing the phosphorus-containing acid and the hindered amine light
stabilizer without solvent; and the like.
[0045] The ratio of the number of phosphorus atoms in the acidic
phosphorus-containing compound to the number of basic nitrogen
atoms in the hindered amine light stabilizer may be in the range of
about 0.05 to about 2, preferably from about 0.25 to about 1.1.
Compositions that contain a large excess of unreacted
phosphorus-containing acidic compounds may result in corrosion of
process equipment during concentrate manufacture and have a
negative effect on the hydrolytic stability of the polymer.
[0046] The salt or salts constituting component (B) of our novel
compositions typically is present in concentrations ranging from
about 0.01 to about 0.25 weight percent based on the total weight
of the composition, i.e., the total weight of the component (A)
polycarbonate, the salt and any additional components present, such
as stabilizers and pigments and colorants. Concentrations of salt
(B) within this range typically are effective to improve the
hydrolytic stability of polycarbonates. The concentration of the
salt(s) preferably is about 0.05 to 0.15 weight percent (same
basis).
[0047] Although polycarbonates are not commonly made using metal
catalysts, it is possible. The polycarbonate may contain metal
catalyst residues in 10 to 200 ppmw. Metal catalyst residues in
concentrations of about 20 to 100 ppmw are more typical. An
addition source of metal catalysts residue may be contributed by a
polymer that is blended with the polycarbonate. For example,
polyesters may contain 10 to 200 ppmw of metal catalyst residues.
Corrosion of metal process equipment is an additional source of
metal contaminants in polycarbonate component (A). For example, 304
and 316 stainless steels contain manganese, chromium and nickel.
The salts of component (B) of the invention can be used in the
polycarbonate compositions where the polycarbonates are either
prepared by use of metal catalysts or contain metal contaminants or
are blended with polymers comprising metal catalyst residues such
that improved hydrolytic stability as well as improved color is
provided to such polycarbonates.
[0048] The acidic phosphorus-containing compounds preferably are
phosphorous acid, phosphoric acid and polyphosphoric acid, most
preferably phosphorous acid.
[0049] Examples of suitable hindered amine light stabilizers (HALS)
include, but are not limited to: Cyasorb UV-3346 (Cytec Industries,
CAS# 90751-07-8), Cyasorb UV-3529 (Cytec Industries, CAS#
19309840-7), Cyasorb UV-3641 (Cytec Industries, CAS# 106917-30-0),
Cyasorb UV-3581 (Cytec Industries, CAS# 79720-19-7), Cyasorb
UV-3853 (Cytec Industries, CAS# 167078-06-0), Cyasorb UV-3853S
(Cytec Industries, CAS# 24860-22-8), Tinuvin 622 (Ciba Specialty
Chemicals, CAS# 65447-77-0), Tinuvin 770 (Ciba Specialty Chemicals,
CAS# 52829-07-9), Tinuvin 144 (Ciba Specialty Chemicals, CAS#
63843-89-0), Tinuvin 123 (Ciba Specialty Chemicals, CAS#
129757-67-1), Chimassorb 944 (Ciba Specialty Chemicals, CAS#
71878-19-8), Chimassorb 119 (Ciba Specialty Chemicals, CAS#
10699043-6), Chimassorb 2020 (Ciba Specialty Chemicals, CAS#
192268-64-7), Lowilite 76 (Great Lakes Chemical Corp., CAS#
41556-26-7), Lowilite 62 (Great Lakes Chemical Corp., CAS#
65447-77-0), Lowilite 94 (Great Lakes Chemical Corp., CAS#
71878-19-8), Uvasil 299LM (Great Lakes Chemical Corp., CAS#
182635-99-0), and Uvasil 299HM (Great Lakes Chemical Corp., CAS#
182635-99-0), Dastib 1082 (Vocht a.s., CAS# 131290-28-3), Uvinul
4049H (BASF Corp., CAS# 109423-00-9), Uvinul 4050H (BASF Corp.,
CAS# 124172-53-8), Uvinul 5050H (BASF Corp., CAS# 199237-39-3),
Mark LA 57 (Asahi Denka Co., Ltd., CAS# 64022-61-3), Mark LA 52
(Asahi Denka Co., Ltd., CAS# 91788-83-9), Mark LA 62 (Asahi Denka
Co., Ltd., CAS# 107119-91-5), Mark LA 67 (Asahi Denka Co., Ltd.,
CAS# 100631434), Mark LA 63 (Asahi Denka Co., Ltd. Co., Ltd. Co.,
CAS# 115055-30-6), Mark LA 68 (Asahi Denka Co., Ltd., CAS#
10063144-5), Hostavin N 20 (Clariant Corp., CAS# 9507842-5),
Hostavin N 24 (Clariant Corp., CAS# 85099-51-1, CAS# 85099-50-9),
Hostavin N 30 (Clariant Corp., CAS# 78276-66-1), Diacetam-5 (GTPZAB
Gigiena Truda, USSR, CAS# 76505-58-3), Uvasorb-HA 88 (3V Sigma,
CAS# 136504-96-6), Goodrite UV-3034 (BF Goodrich Chemical Co., CAS#
71029-16-8), Goodrite UV-3150 (BF Goodrich Chemical Co., CAS#
96204-36-3), Goodrite UV-3159 (BF Goodrich Chemical Co., CAS#
130277-45-1), Sanduvor 3050 (Clariant Corp., CAS# 85099-51-0),
Sanduvor PR-31 (Clariant Corp., CAS# 147783-69-5), UV Check AM806
(Ferro Corp., CAS# 154636-12-1), Sumisorb TM-061 (Sumitomo Chemical
Company, CAS# 84214-94-8), Sumisorb LS-060 (Sumitomo Chemical
Company, CAS# 99473-08-2), Uvasil 299 LM (Great Lakes Chemical
Corp., CAS# 164648-93-5), Uvasil 299 HM (Great Lakes Chemical
Corp., CAS# 164648-93-5), Nylostab S-EED (Clariant Corp., CAS#
42774-15-2). Additional preferred hindered amine light stabilizer
may be listed in the Plastic Additives Handbook 5.sup.th Edition
(Hanser Gardner Publications, Inc., Cincinnati, Ohio, USA,
2001).
[0050] Chimassorb 944 (Ciba Specialty Chemicals, CAS# 71878-19-8),
Cyasorb UV-3529 (Cytec Industries, CAS# 19309840-7), Chimassorb 119
(Ciba Specialty Chemicals, CAS# 106990-43-6) and Tinuvin 770 (Ciba
Specialty Chemicals, CAS# 52829-07-9) as described further herein
in the Examples and any equivalvents thereof are specific examples
of the preferred hindered amine light stabilizers. Chimassorb
119.RTM. is another preferred HALS embodiment. The structure of
Chimassorb 119.RTM. has previously been disclosed also in the
Journal of Materials Science 36 (2001) 4419-4431, incorporated
herein by reference. The chemical name for Chimassorb 119.RTM. as
disclosed in the Journal of Materials Science 36 (2001) at
4419-4431 is 1,3,5-triazine-2,4,6-triamine,
N,N'-1,2-ethane-diyl-bis[[[4,6-bis-[butyl-1,2,2,6,6,-pentamethyl-4-piperi-
dinyl)amino]-1,3,5-triazine-2-yl]amino]-3,1-propanediyl]]bis[N,N"-dibutyl
N,N"bis-(1,2,2,6,6,-pentamethyl-4-piperidinyl)-. A group of
preferred hindered amine light stabilizers include ones having
above formulas (1), (2), (3), (4), (5), (6), (7), (8), (9), (10),
(11) and (12) wherein radical R.sub.7 is hydrogen or alkyl. The
most preferred are high molecular weight HALS wherein the molecular
weight is greater than about 1000 such as Cyasorb UV-3529 (Cytec
Industries, CAS# 193098-40-7). The most preferred HALS correspond
to formula (6) set forth above wherein
R.sub.3=R.sub.4=R.sub.5=R.sub.6=R.sub.7=methyl,
(R.sub.9)(R.sub.10)N-- collectively represent morpholino, L.sub.1
is C.sub.1 to C.sub.6 alkylene, and Z is 1 to 6.
[0051] The term "polycarbonate" as used herein embraces those
polycarbonates comprising repeating units or residues of the
formula 8
[0052] wherein Y is a divalent aromatic or aliphatic radical
derived from a dihydroxyaromatic compound or a dihydroxyaliphatic
compound of the formula HO--Y--OH. Typical dihydroxyaromatic
compounds are 2,2-bis-(4-hydroxyphenyl)propane, also known as
bisphenol A; bis(4-hydroxyphenyl)methane;
2,2-bis(4-hydroxy-3-methylphenyl)-propane;
4,4-bis(4-hydroxyphenyl)heptane;
2,2-(3,5,3',5'-tetrachloro-4,4'-dihydrox- yphenyl)propane;
2,2-(3,5,3',5'-tetrabromo-4,4'-dihydroxyphenol)propane;
3,3'-dichloro-3,3'-dichloro-4,4'-dihydroxydiphenyl)methane;
2,2'-dihydroxyphenylsulfone, and 2,2'-dihydroxylphenylsulfide. Most
preferably, HO--Y--OH is 2,2-bis-(4-hydroxyphenyl)propyl, in which
case, the polycarbonate is a "bisphenol A polycarbonate". Examples
of dihydroxyaliphatic compounds include 1,4-cyclohexanedimethanol,
1,2-propanediol, 1,3-propanediol, 1,4-butanediol,
2,2-dimethyl-1,3-propan- ediol, 1,6-hexanediol,
2,6-decahydronaphthalenedimethanol, 1,2-cyclohexanediol,
1,4-cyclohexanediol, 1,2-cyclohexanedimethanol,
1,3-cyclohexanedimethanol, isosorbide,
4,4'-isopropylidenedicyclohexanol,
2,2,4,4-tetramethylcyclobutane-1,2-diol,
Z,8-bis(hydroxymethyl)-tricyclo-- [5.2.1.0]-decane wherein Z
represents 3, 4, or 5; and diols containing one or more oxygen
atoms in the chain, e.g., diethylene glycol, triethylene glycol,
dipropylene glycol, tripropylene glycol and the like. In general,
these diols contain 2 to 18, preferably 2 to 8 carbon atoms.
Cycloaliphatic diols can be employed in their cis or trans
configuration or as mixtures of both forms. Branched polycarbonates
are also useful in the present invention.
[0053] The polycarbonates comprising component (A) of the
above-described embodiment of the present invention may be prepared
according to known procedures by reacting the dihydroxyaromatic
compound with a carbonate precursor such as phosgene, a haloformate
or a carbonate ester, a molecular weight regulator, an acid
acceptor and a catalyst. Methods for preparing polycarbonates are
known in the art and are described, for example, in U.S. Pat. No.
4,452,933, which is hereby incorporated by reference herein.
[0054] Examples of suitable carbonate precursors include carbonyl
bromide, carbonyl chloride, and mixtures thereof; diphenyl
carbonate; a di(halophenyl)carbonate, e.g., di(trichlorophenyl)
carbonate, di(tribromophenyl) carbonate, and the like;
di(alkylphenyl)carbonate, e.g., di(tolyl)carbonate;
di(naphthyl)carbonate; di(chloronaphthyl)carbon- ate, or mixtures
thereof; and bis-haloformates of dihydric phenols.
[0055] Examples of suitable molecular weight regulators include
phenol, cyclohexanol, methanol, alkylated phenols, such as
octylphenol, para-tertiary-butylphenol, and the like. The preferred
molecular weight regulator is phenol or an alkylated phenol.
[0056] The acid acceptor may be either an organic or an inorganic
acid acceptor. A suitable organic acid acceptor is a tertiary amine
and includes such materials as pyridine, triethylamine,
dimethylaniline, tributylamine, and the like. The inorganic acid
acceptor can be either a hydroxide, a carbonate, a bicarbonate, or
a phosphate of an alkali or alkaline earth metal.
[0057] The catalysts that can be used are those that typically aid
the polymerization of the monomer with phosgene. Suitable catalysts
include tertiary amines such as triethylamine, tripropylamine,
N,N-dimethylaniline, quanternary ammonium compounds such as, for
example, tetraethylammonium bromide, cetyl triethyl ammonium
bromide, tetra-n-heptylammonium iodide, tetra-n-propyl ammonium
bromide, tetramethyl ammonium chloride, tetra-methyl ammonium
hydroxide, tetra-n-butyl ammonium iodide, benzyltrimethyl ammonium
chloride and quaternary phosphonium compounds such as, for example,
n-butyltriphenyl phosphonium bromide and methyltriphenyl
phosphonium bromide.
[0058] The polycarbonate of component (A) also may be a
copolyestercarbonate such as those described in U.S. Pat. Nos.
3,169,121; 3,207,814; 4,194,038; 4,156,069; 4,430,484, 4,465,820,
and 4,981,898, all of which are incorporated by reference
herein.
[0059] Copolyestercarbonates useful in this invention are available
commercially. They are typically obtained by the reaction of at
least one dihydroxyaromatic compound with a mixture of phosgene and
at least one dicarboxylic acid chloride, especially isophthaloyl
chloride, terephthaloyl chloride, or both.
[0060] The present invention provides polycarbonates that exhibit
improved hydrolytic stability. The acidic phosphorus-containing
compound salts of suitable hindered amine light stabilizer
[Component (B)] are useful in providing that hydrolytic
stability.
[0061] Another embodiment of the present invention is a polymer
concentrate comprising:
[0062] (A) at least one polycarbonate; and
[0063] (B) up to about 10 weight percent, preferably about 5 to 10
weight percent, based on the total weight of the polycarbonate of
at least one salt prepared by the reaction of one or more acidic
phosphorus-containing compounds and one or more hindered amine
light stabilizers.
[0064] The compositions of the present invention also may contain
one or more compounds selected from the group consisting of (C)
water, (D) colorants and pigments such as organic colorants,
inorganic colorants and or white pigments such as TiO.sub.2, ZnO
and baryta, (E) other additives such as impact modifiers,
plasticizers, halogenated flame-retardants, fillers, nonhalogenated
flame-retardants, synergists, processing aids, phosphite
stabilizers, phosphonite stabilizers and other stabilizers known to
one skilled in the art; and (F) a recycled polymer.
[0065] The terms "phosphite stabilizers" and "phosphonite
stabilizers" refer to secondary antioxidants that are known to
those skilled in the art and may be represented by the structures
listed on pages 109-112 in the Plastic Additives Handbook 5.sup.th
Edition (Hanser Gardner Publications, Inc., Cincinnati, Ohio, USA,
2001), incorporated herein by reference in its entirety. Some
common phosphite stabilizers are as follows: Ultranox 626 (GE
Specialty Chemicals, CAS# 26741-53-7), Irgafos 168 (Ciba Specialty
Chemicals, CAS# 31570-044), Weston 619 (GE Specialty Chemicals,
CAS# 3806-34-6) and Doverphos S-9228 (Dover Chemicals, CAS#
154862-43-8).
[0066] The term "halogenated flame-retardants" is defined as
compounds that can contain one or more of the following: fluorine,
chlorine, bromine, and iodine, which act in such a way as to
decrease the flammability of the polymer composition. More
preferred are compounds that contain bromine such as brominated
polycarbonate, brominated polystyrene, and the like.
[0067] Salts of phosphorus-containing acids and hindered amine
light stabilizers, as defined herein, may reduce the amount of
corrosion to process equipment as compared to some of the
hydrolysis products of commercial phosphites, phosphorous acid,
phosphoric acid, and polyphosphoric acid, thereby improving the
color of the polymer composition and improving the lifetime of the
process equipment.
[0068] The compositions provided by the present invention are
useful for improving the properties of heavy-gauge sheet, cap
layers for extruded sheet, cap layers for extruded films,
thermoformable sheeting products, injection molded products, thin
films, thick films, articles made using thin films, articles using
from thick films, articles made using heavy gauge sheet, multilayer
films, twin-wall sheet, triple wall sheet and the like.
[0069] This invention is further illustrated by the following
examples of preferred embodiments thereof, although it will be
understood that these examples are included merely for purposes of
illustration and are not intended to limit the scope of the
invention unless otherwise specifically indicated. Unless otherwise
indicated, all weight percentages are based on the total weight of
the polymer composition and all molecular weights are weight
average molecular weights. Also, all percentages are by weight
unless otherwise indicated. Wherever an R group, L group, Y group,
Z group, m group or n group is defined herein, the definition for a
particular group remains the same throughout this description
regardless of whether it is used for multiple formulas or types of
compounds unless otherwise specified.
EXAMPLES
[0070] Experimental Conditions:
[0071] In the examples, the following procedures were followed. To
evaluate the effect of additives on hydrolytic stability of
polycarbonate-polyester blends, samples were cut from 20-mil film
and then exposed to 70.degree. C. and 100% relative humidity by
suspending the films in the vapor space of sealed jars containing a
small amount of water and placed inside a forced air oven set at
70.degree. C. Small samples were subsequently taken periodically
and the molecular weight distribution for the polyester and
polycarbonate components determined using gel permeation
chromatography (GPC). The GPC method for the polycarbonate fraction
consisted of first immersing the blends in tetrahydrofuran to
selectively extract the polycarbonate. The GPC system used to
analyze the polycarbonate fraction consisted of a Perkin-Elmer
LC-250 pump, a Perkin-Elmer LC-600 autosampler, and a Perkin-Elmer
LC-235 photodiode array UV detector operated at 265 nm. The columns
used were a Plgel 5-micron guard, a Mixed-C, and an Oligopore from
Polymer Laboratories. The molecular weight distribution was
computed using monodisperse polystyrene standards for calibration
and the Mark-Houwink constants for polystyrene and polycarbonate
available in the literature. The solvent used for the polyester
fraction was 70/30-v/v hexafluoroisopropanol/methylene chloride
mixture, which is also a good solvent for polycarbonate. The GPC
system used consisted of a Perkin-Elmer LC-250 pump, a Perkin-Elmer
ISS-200 autosampler, and a Perkin-Elmer LC-95 UV/VIS detector
operated at 285 nm. The absorption coefficient of terephthalate
based copolyesters at 285 nm is considerably greater than the
coefficient for polycarbonate so that the method selectively
detects the polyester. The columns used were a Plgel 5-micron guard
and a Mixed-C from Polymer Laboratories. The molecular weight
distribution was computed using monodisperse polystyrene standards
for calibration and Mark-Houwink constants for polystyrene measured
in this solvent. Universal calibration constants for each polyester
were chosen to yield accurate molecular weight values for a series
of samples that were characterized by light scattering
measurement.
[0072] The color of the polymer films is determined in a
conventional manner using a HunterLab UltraScan Colorimeter
manufactured by Hunter Associates Laboratory, Inc., Reston, Va. The
instrument is operated using HunterLab Universal Software (version
3.8). Calibration and operation of the instrument is according to
the HunterLab User Manual and is largely directed by the Universal
Software. To reproduce the results on any colorimeter, run the
instrument according to its instructions and use the following
testing parameters: D65 Light Source (daylight, 6500.degree. K
color temperature), Reflectance Mode, Large Area View, Specular
Included, CIE 10.degree. Observer, Outputs are CIE L*, a*, b*. An
increase in the positive b* value indicates yellowness, while a
decrease in the numerical value of b* indicates a reduction in
yellowness. Color measurement and practice are discussed in greater
detail in Anni Berger-Schunn in Practical Color Measurement, Wiley,
N.Y. pages 39-56 and 91-98 (1994). Preferably, for 20-mil films the
b* value is less than +0.75, more preferably from about +0.25 to
about -0.25.
Examples 1-5
[0073] These examples illustrate the detrimental effect of
commercial phosphite stabilizers on the hydrolytic stability of
polycarbonate-polyester blends. The polyester, polyester A, is a
polyester comprised of 74 mole percent terephthalic acid residues,
26 mole percent isophthalic acid residues and 100 mole percent
1,4-cyclohexanedimethanol residues having an inherent viscosity of
about 0.74 and containing approximately 100 ppmw titanium metal and
the polycarbonate, polycarbonate A, is a bisphenol A polycarbonate
supplied by Bayer as Makrolon 2608. The following commercial
phosphites were utilized: Ultranox 626 (GE Specialty Chemicals,
CAS# 26741-53-7, bis(2,4-di-t-butylphenyl) pentaerythritol
diphosphite), Ultranox 641 (GE Specialty Chemicals, CAS#
26741-53-7, 2,4,6-tri-tert-butylphenyl-2-butyl--
2-ethyl-1,3-propanediol phosphite), Weston 619 (GE Specialty
Chemicals, CAS# 3806-34-6, distearyl pentaerythritol diphosphite)
and Doverphos S-9228 (Dover Chemicals, CAS# 15486243-8,
bis(2,4-dicumylphenyl) pentaerythritol diphosphite). The phosphite
stabilizers were precompounded with polyester A using an 19-mm APV
twin-screw extruder at 250.degree. C., 200 RPM, at a rate of about
5 lbs/hr to produce concentrates containing 5 percent phosphite
stabilizer. Blends of polyester A and polycarbonate A were prepared
by melt blending a 3:1 weight ratio of polyester A with
polycarbonate A, respectively, with 0.5 weight percent of the
various phosphite stabilizers as reported in Table 1. The blends
were prepared as 20-mil extrusion cast films using a 1" Killion
single-screw extruder at 275.degree. C. and 70 RPM. The films were
subsequently conditioned at 70.degree. C. and 100% relative
humidity for up to 3 weeks and the molecular weight of the
polyester A and polycarbonate A components determined by GPC as
previously described. The results are shown in Table 1. As shown in
Table 1, the addition of a phosphite stabilizer improves the blend
color (i.e. less yellow as represented by lower b*); however, the
phosphites are detrimental to hydrolytic stability of the blend as
indicated by significant decrease in molecular weight for both the
polyester A and polycarbonate A components.
1 TABLE 1 20-mil Hydrolytic Stability @ 70.degree. C. and 100%
Relative Humidity CIE Exposure polyester A polyester A
polycarbonate A polycarbonate A Example Phosphite b* (weeks) Mw
.DELTA.Mw (%) Mw .DELTA.Mw (%) 1 No 9.6 0 23297 0.0 13582 0.0
Stabilizer 1 23595 1.3 12446 -8.4 2 23408 0.5 14007 3.1 3 23528 1.0
13391 -1.4 2 Weston -0.1 0 23123 0.0 20723 0.0 619 1 21337 -7.7
14339 -30.8 2 20532 -11.2 12239 -40.9 3 20317 -12.1 9919 -52.1 3
Ultranox 0.5 0 22559 0.0 21684 0.0 626 1 20813 -7.7 14663 -32.4 2
20452 -9.3 12888 -40.6 3 20129 -10.8 11102 -48.8 4 Doverphos 0.4 0
22339 0.0 20935 0.0 9228 1 20937 -6.3 14860 -29.0 2 20112 -10.0
13385 -36.1 3 20641 -7.6 11561 -44.8 5 Ultranox 0.6 0 22651 0.0
20128 0.0 641 1 21367 -5.7 12889 -36.0 2 20461 -9.7 11244 -44.1 3
20574 -9.2 9722 -51.7 Weston 619 is distearyl pentaerythritol
diphosphite. Ultranox 626 is Bis(2,4-di-t-butylphenyll)
pentaerythritol diphosphite. Doverphos 9228 is
Bis(2,4-dicumylphenyll) pentaerythritol diphosphite. Ultranox 641
is 2,4,6 tri-t-butylphenyl 2 butyl 2 ethyl 1,3 propane diol
phosphite.
Examples 6-19
Phosphorous Acid Salts of Hindered Amine Light Stabilizers
(HALS)
[0074] These examples illustrate improved hydrolytic stability for
polycarbonate-polyester blends containing phosphorous acid salts of
HALS compared to blends containing phosphorous acid. The polyester,
polyester B, comprised of 100 mole percent terephthalic acid
residues, 62 mole percent cyclohexandimethanol and 38 mole percent
ethylene glycol residues having an inherent viscosity of about 0.7
and the polycarbonate, polycarbonate B, is a bisphenol A
polycarbonate (tradename Makrolon 1804 (Bayer Corporation) believed
to contain about 0.25 wt % of a ultraviolet light absorbing
compound and a blue toner colorant. A 70:30 ratio by weight blend
of polyester B and polycarbonate B (70:30 blend by weight) were
melt blended with 0.03 weight percent and 0.06 weight percent of
phosphorous acid and the phosphorous acid salts described in Table
2. The phosphorous acid salts were compounded with polyester B
using a WP 30-mm twin-screw extruder at 250.degree. C., 250 RPM at
a rate of about 40 lbs/hr to produce concentrates containing 5
percent of the phosphorous acid salt. The polyester B and
polycarbonate B blends were subsequently prepared as 20-mil
extrusion cast films using a 1" Killion single-screw extruder at
275.degree. C. and 70 RPM.
Example 6
No Stabilizer (Comparative Example)
[0075] A blend was prepared as described previously without any
added stabilizer.
Example 7
Phosphorous Acid (Comparative Example)
[0076] A phosphorous acid concentrate was prepared by mixing
pellets of polyester B with a 45 percent weight percent aqueous
solution of phosphorous acid and then drying under vacuum to
produce a concentrate containing 2.5 percent phosphorous acid.
Blends were prepared as described previously with 0.03 weight
percent and 0.06 weight percent phosphorous acid.
Examples 8-10
Phosphorous Acid Salts of Cyasorb UV-3529
[0077] Phosphorous acid and Cyasorb UV-3529 (supplied by Cytec
Industries, Inc.), which is a polymeric hindered amine light
stabilizer (HALS) believed to conform generally to the compounds of
amine formula (6) set forth above whrein
R.sub.3=R.sub.4=R.sub.5=R.sub.6=R.sub.7=methyl; L.sub.1 is
hexamethylene; and (R.sub.9)(R.sub.10)N-- collectively represent a
morpholino group, were added to a large mortar and pestle according
to Table 2. The solids were ground to a fine powder thereby forming
a salt and placed into a vacuum oven overnight at 70.degree. C.
with a slight ingress of dry nitrogen. The solid was allowed to
cool to room temperature and ground again to a fine powder using
mortar and pestle. Blends were prepared as described previously
with 0.03 and 0.06 weight percent of each phosphorous acid
salt.
2TABLE 2 Example Phosphorous Acid (g) Cyasorb 3529 (g) 8 32.76 200
9 65.45 200 10 98.18 200
Examples 11-14
Phosphorous Acid Salts of Chimassorb 119
[0078] Phosphorous acid and Chimassorb 119 were added to a large
mortar and pestle according to Table 3. The chemical name for
Chimassorb 119.RTM. as disclosed in the Journal of Materials
Science 36 (2001) at 4419-4431 is 1,3,5-triazine-2,4,6-triamine,
N,N'-1,2-ethane-diyl-bis[[[4,-
6-bis-[butyl-1,2,2,6,6,-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2--
yl]amino]-3,1-propanediyl]]bis[N,N"-dibutyl
N,N"bis-(1,2,2,6,6,-pentamethy- l-4-piperidinyl)-. The solids were
ground to a fine powder and placed into a vacuum oven overnight at
70.degree. C. with a slight ingress of dry nitrogen. The solid was
allowed to cool to room temperature and ground again to a fine
powder using mortar and pestle. Blends were prepared as described
previously with 0.03 and 0.06 weight percent of each phosphorous
acid salt.
3TABLE 3 Example Phosphorous Acid (g) Chimassorb 119 (g) 11 37.19
200 12 74.38 200 13 111.57 200 14 148.76 200
Example 15-17
Phosphorous Acid Salts of Tinuvin 770
[0079] To a clean dry 5 L three neck round-bottomed flask equipped
with a mechanical stirrer, thermocouple, heating mantle and
addition funnel was added Tinuvin 770, as described in Table 4 and
1.5 L of isopropyl alcohol. (Tinuvin 770 is a hindered amine light
stabilizer believed to conform generally to the compounds of amine
formula (3) set forth above wherein
R.sub.3=R.sub.4=R.sub.5=R.sub.6=methyl; R.sub.7 is hydrogen;
Y.sub.2 is --OCO--; and L.sub.1 is octamethylene.) The mixture was
heated to 30.degree. C. and stirred until a homogeneous solution
was obtained. To a clean dry 2 L beaker was added phosphorous acid
as given in Table 5 and 1 L of isopropyl alcohol. The mixture was
stirred until a homogeneous solution was obtained. The phosphorous
acid solution was added to the addition funnel and delivered to the
stirred reaction vessel at a rate of about 50 mL/min. A solid
formed as the phosphorous acid solution was added. Stirring was
continued at about 30.degree. C. for 1 h upon complete addition of
the phosphorous acid solution. The reaction mixture was allowed to
cool to room temperature and the product was further precipitated
by adding half of the material to each of two 4 L beakers that
contained 1.5 L of rapidly stirred heptane (equipped with a
mechanical stirrer). The solid material was collected by suction
filtration, washed with 500 mL of heptane, and then allowed to dry
on the filter paper overnight. The solid cake was broken up, placed
into a 12".times.7".times.2" aluminum pan and dried in a vacuum
oven at 70.degree. C. at about 15 mm of Hg with a slight ingress of
dry nitrogen for 2 days. Blends were prepared as described
previously with 0.03 and 0.06 weight percent of each phosphorous
acid salt.
4TABLE 4 Phosphorous Acid Tinuvin 770 Yield Example g (mole) g
(mole) (% of theoretical) 15 450 (0.94) 76.71 (0.94) 90 16 425
(0.88) 106.68 (1.32) 97 17 400 (0.83) 143.20 (1.75) 97
Example 18
Phosphorous Acid Salt of Cyasorb UV-3346
[0080] To a clean dry 5 L three neck round-bottomed flask equipped
with a mechanical stirrer and addition funnel was added 200 g of
Cyasorb UV-3346 (HALS, supplied by Cytec Industries, Inc.) and 1 kg
of toluene. Cyasorb UV-3346 is a polymeric hindered amine light
stabilizer believed to conform generally to the compounds of amine
formula (6) set forth above R.sub.3=R.sub.4=R.sub.5=R.sub.6=methyl;
R.sub.7=hydrogen; L.sub.1 is hexamethylene; and
(R.sub.9)(R.sub.10)N-- collectively represent a morpholino group.
The mixture was stirred until a homogeneous solution was obtained.
To a clean dry 1 L beaker was added 30.69 g of phosphorous acid and
200 g of isopropyl alcohol. The mixture was stirred until a
homogeneous solution was obtained. The phosphorous acid solution
was added to the addition funnel and delivered to the stirred
reaction vessel at a rate of about 13 mL/min. A precipitate began
to form. Stirring was continued for about 30 min upon complete
addition of the phosphorous acid solution. Heptane (1 kg) was added
to the reaction mixture at a dropwise rate to precipitate the
product. The solid material was collected by suction filtration and
washed twice with 100 mL of heptane, then allowed to dry on the
filter paper overnight. The solid cake was broken up, placed into a
12".times.7".times.2" aluminum pan, and dried in a vacuum oven at
70.degree. C. at about 15 mm of Hg with a slight ingress of dry
nitrogen for 24 h to give 230.05 g of material (100% of theoretical
yield). Blends were prepared as described previously with 0.03 and
0.06 weight percent the phosphorous acid salt.
Example 19
Phosphorous Acid Salt of Cyasorb UV-3346
[0081] To a clean dry 5 L three neck round-bottomed flask equipped
with a mechanical stirrer and addition funnel was added 200 g of
Cyasorb UV-3346, which is previously described in Example 18, and 1
kg of toluene. The mixture was stirred until a homogeneous solution
was obtained. To a clean dry 1 L beaker was added 61.37 g of
phosphorous acid and 400 g of isopropyl alcohol. The mixture was
stirred until a homogeneous solution was obtained. The phosphorous
acid solution was added to the addition funnel and delivered to the
stirred reaction vessel at a rate of about 10 mL/min. A precipitate
began to form. Stirring was continued for about 30 min upon
complete addition of the phosphorous acid solution. Heptane (1 kg)
was added to the reaction mixture at a dropwise rate to precipitate
the product. The solid material was collected by suction filtration
and washed twice with 100 mL of heptane, then allowed to dry on the
filter paper overnight. The solid cake was broken up, placed into a
12".times.7".times.2" aluminum pan, and dried in a vacuum oven at
70.degree. C. at about 15 mm of Hg with a slight ingress of dry
nitrogen for 24 h to give 259.09 g of material (100% of theoretical
yield). Blends were prepared as described previously with 0.03 and
0.06 weight percent the phosphorous acid salt.
[0082] The blends described in Examples 6-19 were evaluated for
hydrolytic stability at 70.degree. C. and 100% relative humidity
for up to 6 weeks as described previously. The results for blends
containing 0.03 and 0.06 weight percent phosphorous acid salt are
shown in Tables 5 and 6 respectively. As shown, the addition of
phosphorous acid or phosphorous acid salts of HALS dramatically
improves the color (i.e. less yellow as represented by lower b*) of
polycarbonate-polyester blends compared to the blends without a
phosphorus-containing compound (Example 6). Example 7 serves to
illustrate the detrimental effect of phosphorous acid on the
hydrolytic stability of the blend components similar to the results
shown previously in Examples 2-5 that contained commercial
phosphite stabilizers. However, the hydrolytic stability of the
blend components is significantly improved for the blends
containing phosphorous acid salts of HALS (Examples 8-19) compared
to the blends containing phosphorous acid only (Example 7).
5TABLE 5 Hydrolytic Stability of Blends with 0.03% by weight
phosphorous acid salts Polyester B Polycarbonate B .DELTA.Mw
.DELTA.Mw .DELTA.Mw .DELTA.Mw .DELTA.Mw .DELTA.Mw (%) (%) (%) (%)
(%) (%) Example CIE b* Initial Mw 2 wks 4 wks 6 wks Initial Mw 2
wks 4 wks 6 wks 6 0.9 29111 -0.6 -0.6 -1.9 22415 -5.5 -9.2 -10.5 7
-0.1 28379 -3.0 -6.9 -11.4 21990 -14.3 -34.6 -37.3 8 0.2 30055 0.7
-0.3 -1.7 21453 0.9 -9.0 -12.2 9 -0.1 29695 1.8 0.7 -1.6 20979 0.8
-9.3 -10.2 10 -0.1 29492 1.2 0.4 -1.9 22741 -10.6 -16.8 -18.9 11
0.5 30208 -1.1 -1.2 -2.1 22626 -4.8 -15.0 -13.3 12 03 29089 2.3 1.8
0.1 22191 -6.7 -17.9 -17.5 13 0.2 29321 -0.2 -1.5 -3.1 22220 -4.8
-19.2 -23.0 14 0.0 29067 0.2 -2.1 -4.9 22145 -10.7 -20.1 -23.6 15
0.1 29486 0.5 -0.4 0.0 22370 -11.1 -20.7 -20.0 16 0.0 29376 1.0 0.8
-0.1 22220 -11.9 -19.4 -20.8 17 -0.1 29746 -1.3 -1.0 -2.5 21808
-14.3 -16.6 -30.7 18 0.1 30093 0.6 -1.0 -2.0 22463 -7.5 -14.4 -17.9
19 0.1 29609 1.3 0.7 -2.3 23009 -12.2 -15.0 -17.4
[0083]
6TABLE 6 Hydrolytic Stability of Blends with 0.06 Weight Percent
Phosphorous Acid Salts Polyester B Polycarbonate B .DELTA.Mw
.DELTA.Mw .DELTA.Mw .DELTA.Mw .DELTA.Mw .DELTA.Mw (%) (%) (%) (%)
(%) (%) Example CIE b* Initial Mw 2 wks 4 wks 6 wks Initial Mw 2
wks 4 wks 6 wks 6 0.9 29111 -0.6 -0.6 -1.9 22415 -5.5 -9.2 -10.5 7
-0.2 28477 -12.7 -19.1 -24.7 21518 -27.8 -53.1 -55.4 8 -0.2 29538
1.4 0.2 -0.6 21717 -6.8 -15.0 -15.3 9 -0.2 30029 0.6 -1.6 -3.0
22270 -4.5 -17.1 -16.2 10 -0.1 29518 1.5 0.8 -2.5 23287 -13.8 -21.7
-22.2 11 0.1 29884 0.7 -1.2 -3.0 22665 -13.6 -17.2 -19.3 12 0.0
29535 -0.2 -1.0 -2.9 21764 -3.5 -19.2 -19.1 13 -0.1 29351 -0.8 -2.7
-4.9 21614 -9.6 -16.2 -24.8 14 -0.1 29288 -1.9 -4.8 -9.9 22072
-16.6 -27.1 -31.0 15 0.0 29465 0.4 -0.2 -0.4 23459 -21.4 -27.8
-31.3 16 -0.1 29269 0.9 0.6 -1.2 21965 -12.1 -23.8 -29.8 17 -0.1
29189 0.8 1.2 -2.1 22114 -24.4 -30.6 -33.7 18 0.1 29962 -0.4 0.2
-2.6 22278 -4.1 -12.0 -15.5 19 -0.1 29864 0.3 -1.3 -2.3 22057 -4.5
-9.7 -18.4
Examples 20-22
Phosphorous Acid Salts Prepared by Mechanical and Organic
Methods
[0084] These examples illustrate different methods of preparing the
phosphorous acid salts. To a clean, dry 5 L three neck
round-bottomed flask equipped with a mechanical stirrer and
addition funnel was added 100 g of Cyasorb UV-3529, which is
described in Examples 8-10, and 575 g of toluene. The mixture was
stirred until a homogeneous solution was obtained. To a clean dry 2
L beaker was added 28.05 g (0.34 mol) of phosphorous acid and 575 g
of isopropyl alcohol. The mixture was stirred until a homogeneous
solution was obtained. The phosphorous acid solution was added to
the addition funnel and delivered to the stirred reaction vessel
over 2 h (added dropwise). Stirring was continued for about 30 min
upon complete addition of the phosphorous acid solution. The
reaction product was precipitated by adding half of the reaction
mixture to each of two 4 L beakers that contained 2475 g of rapidly
stirred heptane (equipped with a mechanical stirrer). The solid
material was collected by suction filtration and washed with 500 mL
of heptane then allowed to dry on the filter paper overnight. The
solid cake was broken up, placed into a 12".times.7".times.2"
aluminum pan and dried in a vacuum oven at 70.degree. C. at about
150 torr with a slight ingress of dry nitrogen for 24 h to give
135.07 g of material (>100% of theory, slightly solvent
wet).
[0085] Blends of polyester B and polycarbonate B (70:30 blend ratio
by weight) were melt blended along with 0.1 weight percent of the
phosphorous acid salt prepared by an organic method (Example 20),
the phosphorous acid salt prepared by a mechanical method described
in Example 9 (Example 21) and Weston 619 (Example 22) for
comparison. The phosphorous acid salts and Weston 619 were
compounded with polyester B using a 30-mm WP twin-screw extruder at
250.degree. C., 250 RPM at a rate of about 40 lbs/hr to produce
concentrates containing 5 percent of each additive. The blends were
prepared as 20-mil extrusion cast films using a 1" Killion
single-screw extruder at 275.degree. C. and 70 RPM. The blends were
evaluated for hydrolytic stability at 70.degree. C. and 100%
relative humidity for up to 6 weeks as described previously and the
results are shown in Tables 7. The results show significantly
improved hydrolytic stability for the blends containing the
phosphorous acid salts whether prepared by an organic method
(Example 20) or a mechanical method (Example 21) compared to the
commercial phosphite stabilizer Weston 619 (Example 22).
7 TABLE 7 Polyester A Polycarbonate A .DELTA.Mw .DELTA.Mw .DELTA.Mw
.DELTA.Mw .DELTA.Mw .DELTA.Mw Initial (%) (%) (%) Initial (%) (%)
(%) Example Mw 2 wks 4 wks 6 wks Mw 2 wks 4 wks 6 wks 20 27105 -1.7
-3.1 7.3 23287 -8.4 -21.6 -25.5 21 26159 1.1 -0.8 7.9 22538 -8.1
-18.2 -24.0 22 25957 -6.4 -9.1 -8.5 22308 -25.7 -40.3 -49.0
[0086] The invention has been described in detail with particular
reference to preferred embodiments thereof, but it will be
understood that variations and modifications can be effected within
the spirit and scope of the invention.
* * * * *